This study presents the first feasibility evaluation of a lab-scale thermophilic anaerobic membrane distillation bioreactor (AnMDBR) for treating sugarcane vinasse, considering the use of waste heat from vinasse which comes from ethanol distillation at high temperatures (80–90 °C). This research focuses mainly on evaluating the VFA production and recovery from anaerobically digested sugarcane vinasse in a single-stage An-MDBR system, alongside monitoring the generation of bioCH4, another bioproduct. The AnMDBR was fed with raw vinasse (phase I) and with ultrafiltered vinasse (phase II). The ultrafiltration of the sugarcane vinasse as pre-treatment stage resulted in a reduction in the COD/SO42- ratio, adversely impacting process performance. The system achieved high removal efficiencies of COD (98 ± 1 % when fed with raw vinasse, and 94 ± 4 % with ultrafiltered vinasse), phosphorus (almost 100 %) and ammonia nitrogen (∼91 %). Regarding byproducts, the system showed low efficiencies in the VFAs recovery in the distillate and low methane content of the biogas formed. To enhance the VFA recovery, the pH of the solution should be kept below the pKa values favoring the VFA transport across the membrane. The permeate flux exhibited a decline throughout operation (from 4.4 to 0.5 L/(m2·h)), attributed to the fouling layer formation. Thus, strategies to mitigate membrane fouling are crucial for improving permeate flux and, consequently, enhancing the feasibility of full-scale MDBR for sugarcane vinasse treatment.